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Lecture 11

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
pearl necklace
pearl necklace
Polymers

You may think of polymers as being a relatively


modern invention however naturally occurring
polymers have been used for thousands of years
– wood, rubber, cotton, wool, leather, silk,.. etc
• Artificial polymers are, indeed, relatively
recent and mostly date from after WWII
in many cases, the artificial material is both
better and cheaper than the natural alternative

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A polymer is a large molecule made by linking together
repeating units of small molecules called monomers

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Polymers
A macromolecule is a very large molecule consisting of repeating units called monomers.
These structural units are bound together by covalent bonds.

A collection of macromolecules is called a polymer. For example, polyethylene

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Polymerization

Polymers are prepared by polymerizing a monomer. The reaction is called polymerization

Polymerization of ethylene to form polyethylene

Ethylene monomer units

H 2C CH2 -CH2CH2-CH2CH2-CH2CH2-CH2CH2-
ethylene

polyethylene

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Some Important Terms
• Degree of polymerization: The number of repeating
units present in a polymer is called degree of
polymerization.
• “n” is called degree of polymerization. When n is large,
the polymers are called high polymers. For low values of
n, less than 10, the polymers are called oligomers.
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Lecture 12

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Classification of polymers

1. Natural and Synthetic Polymers:


(Based on occurrence)

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
2. Thermoplastic and thermosetting polymers (Based on thermal
behavior)
3. Addition and condensation polymers (Based on polymerization
reaction)

Fig. Examples of addition polymers.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
4. Linear, branched and cross-linked polymers (Based on
chemical structure)
5. Organic and inorganic polymers (Based on backbone material)
6. Atactic, isotactic and syndiotactic polymers (Based on Stereo
chemistry)

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Based on mechanical behavior
7. Elastomers (undergo elongation on pulling and return to
original length when relesed, Ex- rubber)
Fibers (long, thin, thread like, Ex- jute, wood, silk)
Resins (low MW polymer used as adhesive)
Plastics (which can be molded onto desired shape)

8. Homopolymers and copolymers

Fig. Homopolymers and Copolymers

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Classification of polymers

1. Natural and Synthetic Polymers: (Based on occurrence)


Natural polymers: wood, cellulose,, jute, cotton, wool etc.
Synthetic polymers: PE, PVC, epoxy resin etc.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
2. Thermoplastic and thermosetting polymers
(Based on thermal behavior)
Thermoplastic polymers: The polymers that soften on
heating and which can be converted into any shape on
cooling are called thermoplastics. The process of heating,
reshaping, and retaining the shape on cooling can be
repeated several times without affecting their properties
much. Ex: PE, PolyCarbonate(PC), Polytetrafluoro ethylene
(PTEE) etc.
Thermosetting polymers: Polymers that undergo chemical
changes and cross-linking on heating and become
permanently hard, rigid and infusible on cooling, are called
thermosetting polymers. They do not soften on reheating;
instead they undergo degradation. Ex: phenol-formaldehyde
(bakelite), urea-formaldehyde etc.
3. a) Addition polymers (Based on type of polymerization)
The polymers formed by self-addition of several monomers to
each other without elimination of byproducts are called
addition polymers. Ex: PVC, PE etc.

•Features:
•Monomers add successively to a growing polymer chain
•Polyethylene and polystyrene are addition polymers.
•Only olefinic or vinyl compounds can undergo addition polymerization.
•No elimination of byproducts.
•Double bond provides required bonding sites.
•The elemental composition of the polymer is the same as that of monomer.
•The addition of monomers takes place rapidly.
•Polymerization is brought about by initiators like free radicals.
Addition Polymerization Example

In this type of polymerization C=C bonds of monomers react to form larger


monomers until the unit is a larger polymer chain as seen here.

Table on the next slide shows ethylene monomer based polymers

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Fig. Examples of addition polymers.
3. b) Condensation Polymer (Based on type of
polymerization)
The polymers formed by intermolecular condensation reaction by the functional
groups of monomers with continuous elimination of small molecules such as
ammonia, water etc. Ex: nylon-6,6; polyester etc.

•Polymer chain grows when monomers combine and split out water or other small
molecule.
•Nylon 6,6 and polyurethane are condensation polymers.
•The monomers having two or more reactive functional groups can undergo
condensation polymerization.
•There is continuous elimination of byproducts.
•Polymerization proceeds through intermolecular condensation.
•Polymerization is catalyzed by acids or alkali.
•The polymer chain built up is slow and stepwise.
•The elemental composition of the polymer is different from that of the
monomers.
Condensation Polymer Example
4. Linear, branched and cross-linked polymers (Based
on chemical structure)

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5. Organic and Inorganic polymer

Organic

Inorganic
6. Atactic, isotactic and syndiotactic polymers (Based on
stereochemistry)

Side Group is random

Side Groups are on same side

Side Groups are on


alternating fashion
Fig. Atactic, isotactic and syndiotactic polymers.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Homo Polymerization Example

In this type of polymerization C=C bonds of monomers react to form larger


monomers until the unit is a larger polymer chain as seen here.

Table on the next slide shows ethylene monomer based polymers

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Copolymerization
The polymerization of two or more different monomers resulting in the formation
of a polymer containing both monomers linked in one chain is called
copolymerization. It is considered as a type of addition polymerization. The polymers so
formed are called copolymers.
A copolymer is a polymer that has two types of monomer units in its chain .
•Block copolymer: When repeating units of each kind appear in blocks, it is called a
block copolymer.
•Random copolymer: If the various repeating units occur randomly along the chain
structure, the polymer is called a random copolymer.
•Graft copolymers: They are formed when chains of one kind are attached to the
backbone of a different polymer.
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Lecture 13

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Structure-property relationship
The Structure of the polymers depends upon:
1. Size and shape of the polymer chain .
2. Chemical nature of the monomers.

The Structure of the polymers further effects the physical and mechanical
properties of polymers.
• Strength
• Crystalinity
• Elasticity
• Non-elastic Nature of Fibers
• Plastic deformation
• Chemical Resistivity
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The tensile strength of a material
quantifies how much stress the
material will endure before
suffering permanent deformation.
For example, a rubber band with
a higher tensile strength will hold
a greater weight before snapping
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For a polymer to be commercially useful , It should have low melt
viscosity, high tensile strength and impact strength.

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Crystallinity

Amorphous and crystalline regions in a polymer. The crystalline region


(crystallite) has an orderly arrangement of molecules. The higher the 35
crystallinity, the harder, stiffer.
Crystallinity

Linear polymers have higher crystallinity, because the atoms along the chain
Permit closer approach, branched polymer will have low crystallinity.

Polymers containing polar groups can form H-bonding, so have higher


crystallinity.

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• Elasticity: Elasticity of a polymer is due to uncoiling and
recoiling of the molecular chains on application of force. For
a polymer to show elasticity, the individual chains should not
break on prolonged stretching. Breaking takes place when
the chains slip past each other and get separated. Elasticity
can be increased by
1. Cross linking
2. Avoiding bulky groups

• Non-elastic Nature of Fibers : Here chain mobility is


reduced by very close packing of the polymer chain
backbone without cross linking. Polar groups and cyclic
rings in the backbone chain give high strength to polymer
fibre. Ex. In Nylon 6,6 and Poly Ethylene Terephthalate
(PET)
• Plastic deformation : It is studied by applying heat and P. Thermoplastic
polymer on applying heat and P first become soft, flexible and undergo
deformation. On further heating above their M.P they melt and flow.
Such a property is called plastic deformation. On cooling they returned
to original state.
• On the other hand thermosetting polymers do not show deformation
because On strong heating they undergo degradation.

• Chemical Resistivity: It depends upon structure of polymer and nature


of attacking reagents. During chemical attack it first softens, swells and
losses its strength and then dissolves. It depends on
• Presence of polar-non polar group, decides their solubility.
• Molar mass higher, lower solubility.
• Degree of crystallinity higher, resistivity higher.
• Extent of cross linking higher, resistivity higher.
Glass transition temperature and
melting point

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Hhigher flexibility, lower Tg,
less side group- more flexible- lower Tg,
Sstronger intermolecular force-higher Tg

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Thank You
Lecture 14

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Some Important Commercial Thermoplastics

Polythylene (PE): LDPE and HDPE Low and high density


LDPE: Lots of branching-
Used in Food packaging

HDPE: No branching- Used for


Cans, milk bottle, fuel tank.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Polypropylene

Application:-
For making packaging container, furniture and toys.

Me3Al +TiCl4= Ziegler –Natta catalyst


Polystyrene

Used in making video cassettes,


radio and television parts.

Polyvinylchloride

Used in making cable insulator,


Rigid pipes etc.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Polyvinyl Acetate

Used in making adhesive for textiles, paper


and woods.

Polytetrafluoroethylene/Teflon

Used for insulation of coil, capasitor, wires.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Polymethyl Methacrylate/Plexiglass

Used in making aircraft window.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
7. Elastomers, fibers, resins and plastics
Elastomers: Polymers that undergo very long elongation
when pulled apart and return to their original length on
release are called elastomers. Ex natural rubber, silicone
rubber etc.
Fibres: These are long, thin and thread-like ploymers. Ex:
jute, wood, silk etc.
Resins: These are low molecular weight polymers used as
adhesives. They can be in the form of liquids or powders.
Ex: phenol-formaldehyde, urea-formaldehyde etc.
Plastics: These are polymers which can be molded into
desired shapes by the application of heat and pressure.
Ex: PE, PVC etc.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Elastomers (Rubber)

Natural rubber is prepared from latex of Hevea rubber trees or


gutta-percha and balata. It is a linear polymer of isoprene and is called
polyisoprene.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Amino Resins

Urea–Formaldehyde Resin

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Some Important Synthetic and Semi-synthetic Fibers

Nylons (polyamides) are polyamide.

Application: Making sports gear, fishing lines, sports equipments


Making brushes and combs.

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Lecture 15

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.
Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are
organic polymers that conduct electricity. Such compounds may have metallic conductivity
or can be semiconductors

Examples

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Fabrication of polymers

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Injection Molding
Extrusion Molding

Extrusion molding is a manufacturing process used to


make pipes, hoses, drinking straws, curtain tracks, rods, and fiber.
The granules melt into a liquid which is forcibly passed through a die,
forming a long 'tube like' shape. The shape of the die determines the
shape of the tube. The extrusion is then cooled and forms a solid
shape. The tube may be printed upon, and cut at equal intervals. The
pieces may be rolled for storage or packed together. Shapes that can
result from extrusion include T-sections, U-sections, square sections,
I-sections, L-sections and circular sections.
Extrusion Molding
> Raw materials in the form if thermoplastic pallets, granules, or
powder, placed into a hopper and fed into extruder barrel.

> The barrel is equipped with a screw that blends the pallets and
conveys them down the barrel

> Heaters around the extruder’s barrels heats the pellets and liquefies
them

>>>Screw has 3-sections

Feed section
Melt or transition section
Pumping section.
Plastic Extruder
Advantages:
1. Low initial setup cost
2. Fast set up time.
3. Low production cost.

Applications:
Used for manufacturing Solid rods, channels, tubing,
pipe, window frames, architectural components can be
extruded due to continuous supply and flow.

• Plastic coated electrical wire, cable, and strips are also


extruded
MCQs_Polymers
Q.1: Which of the following is not a natural polymer?
a) natural rubber
b) cis-polyisoprene
c) trans-polyisoprene
d) trans-polyacetylene
Q.2: Which of the polymer undergo reversible changes on heating?
a) Bakelite
b) PVC
c) Both a & b
d) Phenol-Formaldehyde polymer
Q.3. Which of the following polymer is formed from condensation polymerization?
a) Nylon 6,6
b) Urea-Formaldehyde resin
c) Thermosetting plastic
d) All of these
Q.4. Phenol-Formaldehyde resin is the type of
a) Linear polymer
b) Branched polymer
c) Network polymer
d) Block polymer
Q.5. Functionality of monomer means
a) functions of monomer
b) functions of polyomer
c) number of repeating units
d) total number of bonding sites
Q.6. Which of the following molding technique is used for thermosetting
polymers?
a) Injection molding
b) Extrusion molding
c) Both a& b
d) Compression molding
Q.7. Ebonite is
a) less vulcanized rubber
b) high vulcanized rubber
c) natural rubber
d) gutta-percha rubber
Q.8. Which of the following is a Step growth polymer?
a) Teflon
b) PVC
c) both a & b
d) Bakelite
Q.9. Choose the correct name for monomer of natural rubber
a) acetylene
b) methane
c) isoprene
d) ethylene
Q.10. For a macromolecule tacticity is the study of:
(a) Crystallinity
(b) Stereochemistry
(c) Molecular weight
(d) Degree of polymerization
11. vulcanized rubber has
(a) good tensile strength (b) bad tensile strength (c) conducting property
(d) low durabilit
12.Conducting polymer is used in - (a) display device (b) light emitting
diodes (c) information storage device (d) all of these
13. Polyacetylene is a (a) non conductive polymer (b) conducting
polymer (c) composite material (d) none of these
14. Which type of polymer is used in light emitting diodes- (a)
conducting (b) non conducting (c) vulcanized rubber (d) teflon
15. Nylon 6.6 is used in (a) fishing lines (b) sports equipment (c) combs
(d) all of these
16. HDPE is a (a) homo polymer (b) copolymer (c) conducting polymer (d)
none of these
17. Drinking straw is made by (a) extrusion molding (b) injection
molding (c) compression molding (d) none
18. Compression molding is usually used for (a) thermoplastic (b)
thermosetting (c) both a and b (d) none of these
19. Phenol-formaldehyde resin is a (a) homopolymer (b) copolymer (c)
both homo and co polymer (d) none of these
20. Polystyrene is (a) homopolymer (b) copolymer (c) composite material
(d) none of these
Thank You